CN1116290C - Process for preparing tetrahydrofuran from dialkoxybutenes - Google Patents

Process for preparing tetrahydrofuran from dialkoxybutenes Download PDF

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CN1116290C
CN1116290C CN97192054A CN97192054A CN1116290C CN 1116290 C CN1116290 C CN 1116290C CN 97192054 A CN97192054 A CN 97192054A CN 97192054 A CN97192054 A CN 97192054A CN 1116290 C CN1116290 C CN 1116290C
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butylene
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CN1210526A (en
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R·菲施尔
R·宾考斯
M·沙非尔
A·霍恩
P·施瓦布
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/32—Preparation of ethers by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • C07D307/08—Preparation of tetrahydrofuran

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  • Furan Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention concerns a process for preparing tetrahydrofuran by reacting 1,4-butene diol diethers of formulae (I) -RO-CH2-CH=CH-CH2-OR and/or (II) -RO-CH2-CH2=CH-CH2-OR, in which the R groups can be identical or different and stand for C1-C15 alkyl or cycloalkyl groups, C6-C12 aryl groups or C7-C15 aralkyl groups, with water and hydrogen at temperatures of between 20 and 300 DEG C and a pressure of between 1 and 300 bar in the presence of catalysts or catalyst combinations which both contain components which can hydrogenate and comprise acid or basic centres. The invention further concerns a novel process for preparing the 1,4-butene diol diethers of formula (I) by metathesis.

Description

Prepare tetrahydrofuran (THF) by the dialkoxy butylene
The present invention relates to a kind ofly in the presence of catalyzer or catalyst composition, prepare the method for tetrahydrofuran (THF) by dialkoxy butylene and water and H-H reaction, this catalyzer has the hydrogenation ability and acidity is arranged or basic center.
Industrial, by 1, the cyclisation of 4-butyleneglycol comes mass preparation tetrahydrofuran (THF) (Weissermel, Arpe industrial organic chemistry, the 4th edition, the Weinheim of VCH press, 1994,111 pages).The possible method of another preparation tetrahydrofuran (THF) is dihydrofuran hydrogenation (EP-A 524 216).
In these cases, precursor raw material is acetylene, propylene or propylene oxide, cis-butenedioic anhydride or divinyl.Because divinyl is easy to obtain, so the preferential now novel method of being set out by divinyl of seeking so that prepare tetrahydrofuran (THF) with simpler mode and lower expense, particularly reduces the number of reactions steps.
Intermediate based on the divinyl raw material is the dialkoxy butylene, and they can be 1,4-dialkoxy-2-butylene (cis with trans) and 1,4-dialkoxy-1-butylene.
Their available following general formulas are represented
RO-CH 2-CH=CH-CH 2-OR I and RO-CH 2-CH 2In-CH=CH-OR II the formula, R is identical or different C 1-C 15Alkyl or cycloalkyl, C 6-C 12Aryl or C 7-C 15Aralkyl.
1 of formula I and II, 4-butyleneglycol diether can be used prepared in various methods, for example by dibromo butene and 2 normal alcohol reactions, add on the divinyl (SU-A 1046238 or EP-A 462 031) or add to (WO-A 8,902 883) on the vinyl oxyethane by alcohol by pure oxidation.
The same other method relevant with the present invention comprises, alcohol is added on the divinyl, generates monoalkoxy butylene (disclosed as WO 95/19334), and latter's transposition becomes dialkoxy-2-butylene and 2-butylene then.
We find, as 1 of formula I and/or formula II, 4-butyleneglycol diether is under 20-300 ℃, 1-300 crust, and in the presence of following catalyzer or catalyst composition during with water and H-H reaction, available step seldom makes the tetrahydrofuran (THF) of fine productive rate from divinyl,
RO-CH 2-CH＝CH-CH 2-OR I
RO-CH 2-CH 2-CH＝CH-OR II
In the formula, R can be identical or different, is C 1-C 15Alkyl or cycloalkyl, C 6-C 12Aryl or C 7-C 15Aralkyl.Catalyzer contains and possesses the hydrogenation ability and acidity is arranged or the component of basic center.
Imagining reaction of the present invention can be undertaken by the following single step that illustrates:
The alcohol of cancellation can be used to prepare starting compound I and II also is possible.
The following information of the single step of relevant imagination can obtain in the literature:
Though dialkoxy-2-butylene isomery becomes corresponding dialkoxy-1-butylene not describe.But two trimethyl silyl 2-butylene ethers become two trimethyl silyl 1-butylene ether (communication of C.Malange et al. tetrahedron, 36) 1995 (1133-1136) to be considered to similarly with the nickelous cyanide isomery.
Dialkoxy-1-butylene is hydrolyzed into corresponding alcohols and aldehydes ether and does not know, has only the example (following Okuyama et al., Journal of the American Chemical Society, 89 (1967) 5826-5831) of simple enol ether acid-catalyzed hydrolysis in the document.
Described aldehyde ether and be hydrogenated into corresponding 4-alkoxyl group butanols as catalyzer (only being used as alkoxy compound), on an acidic catalyst, be cyclized into tetrahydrofuran (THF) (THF) (EP 18164B1) subsequently at the alkylating compound in α position with Raney nickel.But in this case, ether component not only conduct is pure by cancellation, and as dewatered product such as alkene are by cancellation accordingly, they are recycling in cyclization process, but certain difficulty is arranged.Because economic cause, it is preferred utilizing again.If generation alkene, then THF is not a primary product, and 1, the 4-butyleneglycol is a primary product, and only just generates THF after the water cancellation.
According to above-mentioned prior art, it is shocking, might prepare THF with a step or maximum two step highly selectives by the dialkoxy divinyl of formula I and II, obtain alkoxide component (therefore the round-robin possibility is arranged and form a kind of circulation technology) simultaneously.
Reaction can be undertaken by a step or two steps.
In single stage method, the compound of formula I and/or II reacts in gas phase or liquid phase, in the presence of water and hydrogen and catalyzer, obtains THF and alcohol.This catalyzer has the hydrogenation ability and Br nsted acid is arranged and/or Lewis acid or alkali center, perhaps for being added with the suitable catalyzer of Br nsted acid and/or Lewis acid or alkali.
It is different that precursor and R group in the intermediate can be, but be preferably identical.The preferred group that uses is those genes that can obtain primary alconol after the cancellation effect.
In two-step approach, or the compound of I and/or II reacts in the presence of water and hydrogen and hydrogenation catalyst, makes 1,4-butyleneglycol monoether, and the latter has intermediate purification or changes into THF and alcohol without intermediate purification, on acidity or basic catalyst.
Single stage method or two-step approach can intermittently be carried out, and preferably carry out continuously.
Following method characteristics are applicable to the first step in single stage method and the two-step approach:
1 of water and formula I and/or II, the mol ratio of 4-butyleneglycol diether is 100: 1, preferred 50: 1, particularly 10: 1.
Mainly the reaction pressure by the hydrogen decision is 1-300, preferred 1-200, particularly 1-100 crust, and temperature of reaction is 20-300, preferred 40-270, particularly 80-200 ℃.
Being specially adapted to catalyzer of the present invention is that those can make ketone or aldehydes and hydrogen catalysis hydrogenation generate the catalyzer of alcohols.Usually, they contain one or more elements or its compound in periodictable I, II, VI-VIII subgroup or the III-V main group.Catalyzer can be homogeneous phase solution (example is in following document: H.Kropf, organic chemistry method (Houben-Weyl), volume IV/IC, Georg Thieme press, Stuttgart, 1980,45-67 page or leaf) or heterogeneous catalyst.
The example of preferred homogeneous catalyst is the complex compound of rhodium, ruthenium, iridium, palladium, platinum and cobalt and phosphine or phosphite ligands, and its preparation method is for example in that (A-A 727641, H.Brunner in Hartley: the chemistry of metal-carbon key; Volume 5,110-124 page or leaf, JohnWiley ﹠amp; Sons, people such as New York 1989 and Toth, Chinese Journal of Inorganic Chemistry (Inorg.Chim Acta) 42, (1980) 153 and their documents of drawing in describe.In addition, the metal complex of Shi Heing is also open at WO 95-193344.
The Ru complex compound is particularly preferred.The example that can mention be HRuCl (CO) (TPP) 3And H 2Ru (CO) (TPP) 3(TPP=triphenylphosphine).
Heterogeneous catalyst can be fixed and use or move use, for example in fluidized-bed reactor or in use in suspension.Its example is for example at Houben-Weyl, and the organic chemistry method is described in the volume IV/IC 16-26 page or leaf.
Preferably those contain the catalyzer of one or more Ib, IIb, VIb, VIIb and VIII family element, particularly copper, chromium, rhenium, cobalt, rhodium, nickel, palladium, ruthenium, iridium and platinum or its compound in these hydrogenation catalysts.
The catalyzer of Shi Yonging for example can be those catalyzer of so-called precipitated catalyst in the methods of the invention.This class catalyzer can prepare with following steps: by adding the oxyhydroxide and/or the carbonate of basic metal and/or alkaline-earth metal, make catalytic active component from its salts solution, particularly from nitrate and/or acetate solution, be precipitated out, as coming out as sl. sol. oxyhydroxide, oxide hydrate, subsalt or carbonate deposition; The subsequent drying throw out; By 300-700, particularly 400-600 ℃ of following roasting, they are changed into corresponding oxide compound, mixed oxide and mixed valence oxide compound then; The latter handles with hydrogen or hydrogen-containing gas under 50-700, particularly 100-400 ℃, is reduced into the oxygenated compound of corresponding metal and/or low-oxidation-state, and changes into actual catalytic activity form.Usually, this reduction process is performed until not till the regeneration water.In the preparation of the precipitated catalyst that contains solid support material, the precipitation of catalytic active component can be carried out in the presence of the related vector material.But catalytic active component can be that those are deposited on the metal of the shortening on the solid support material or the catalyzer of metallic compound at the solid support material hydrogenation catalyst that precipitates, is preferred for the inventive method simultaneously sedimentary from associated salts solution preferably also.Except containing catalytic active component, above-mentioned precipitated catalyst also contains a kind of like this solid support material that also is applicable to the inventive method in addition, has the component of catalytic hydrogenation activity for example to be applied on the solid support material by pickling process in them.
The method that catalytically-active metals is applied on the carrier is unimportant usually, can in all sorts of ways and finish.For example available following steps with catalytically-active metals be applied on the carrier, with the salt of coherent element or the solution or the suspension impregnation of oxide compound; Dry; Then with reductive agent, preferably metallic compound is reduced into the relevant metal or the compound of low-oxidation-state with hydrogen or complicated hydride.Another possible method that catalytically-active metals is applied on the carrier may further comprise the steps: with being easy to carry out pyrolysated salts solution such as nitrate solution or with the solution such as the carbonylcomplex of catalytically-active metals or the solution impregnating carrier of hydrido complex that are easy to carry out the pyrolysated complex compound; To heat down at 300-600 ℃ through the carrier of dipping, so that make the metallic compound thermolysis of absorption, this thermolysis is preferably carried out under protective atmosphere.The example of the protection gas that is fit to is nitrogen, carbonic acid gas, hydrogen or rare gas element.
Catalytically-active metals also can be deposited on the support of the catalyst by vapour deposition process or flame spraying.For the success of the inventive method, the content of catalytically-active metals on these supported catalysts is unimportant in principle.For those skilled in the art, the content that the advantages of high catalytic activity metal content is lower in these supported catalysts can obtain higher transformation efficiency when empty, and this point is self-evident.Usually, by whole catalyzer, used supported catalyst contains 0.1-90, preferred 0.5-40% (weight) catalytically-active metals.Because described content is based on the whole catalyzer that comprises solid support material, but different solid support materials has different proportion and specific surface, and it also is possible that content fluctuates up and down in this scope, and method of the present invention is not had detrimentally affect.Certainly, multiple catalytically-active metals being applied to also is possible on the specific support material.In addition, it is possible for example with the method for DE-A 2519817, EP-A 1477219 and EP-A 285420 catalytically-active metals being applied on the carrier.In the catalyzer of these patent disclosures, catalytically-active metals is as thermal treatment and/or reduce the alloy that macerate that the salt of above-mentioned metal or complex compound dipping obtain generates and exist.
The activation of precipitated catalyst and supported catalyst also can be carried out with the hydrogen original position that exists when the reaction beginning, but the preferably activation separately before use of these catalyzer.
The oxide compound of common aluminium, the titanium dioxide zirconium, silicon-dioxide, argilla if you would take off soil, silicate such as Magnesium Silicate q-agent or pure aluminium silicate, zeolite such as ZSM-5 or ZSM-10 zeolite and gac can be used as solid support material.Preferred solid support material is aluminum oxide, titanium dioxide, silicon-dioxide, zirconium dioxide and gac.Certainly, using the different carriers mixtures of material also is possible as support of the catalyst of the present invention.
The example of the heterogeneous catalyst that is used for the inventive method that can mention is as follows: platinum/gac, palladium/gac, palladium/aluminum oxide, cobalt/gac, cobalt/silicon-dioxide, cobalt/aluminum oxide, iron/gac, magnesium/gac, rhenium/gac, rhenium/silicon-dioxide, rhenium/tin/gac, rhenium/palladium/gac, copper/gac, Cu/SiO 2, copper/aluminum oxide, copper chromite, chromous acid barium copper and at DE-A3 932332, US-A 3449445, EP-A 44444, EP-A 147 219, DE-A 3904083, DE-A2321101, WEP-A 415 202, disclosed catalyzer among DE-A 2 366 264 and the EP-A 100406.
Particularly preferred catalyzer contains in metallic copper, ruthenium or the rhenium at least a.
For gas-phase reaction, Br nsted acid and/or Lewis acid or alkali can be applied on the catalyzer; And for liquid phase reaction, they also can be the homogeneous phase solution form.Br nsted acid and/or Lewis acid are preferred.Preferred acid or the alkali that uses is as follows.
If reaction is carried out in two steps, the effluent of the first step-if suitable, remove catalyzer after-can directly separate or preferred fractionation by distillation becomes alkoxide component, if suitable excessive water and 4-alkoxyl group butanols, the latter is used further to discharge THF in gas phase or liquid phase.
The cyclisation that generates THF and alcohol can be on homogeneous or heterogeneous basic catalyst, preferably carry out at homogeneous or heterogeneous an acidic catalyst.
The example of basic catalyst is alkali-metal or the oxide compound of alkaline-earth metal or oxyhydroxide or contain the solid support material of these basic components, and is for example dipping or spraying or the alkali ion exchange.
The example of an acidic catalyst be H type zeolite, acid ion exchangers, heteropolyacid, tart and superpower acidity metal oxide-if suitably, their available vitriol or phosphoric acid salt mix, and mineral acid or organic acid.
The example of the zeolite that is suitable for is the mordenite class, or the erionite of aperture or chabazite, faujusite such as Y-, X-or L-zeolite.This class faujusite also comprises faujasite-type " super steady " zeolite, the i.e. zeolite of dealuminzation.
Particularly preferred zeolite is the zeolite of those five-membered ring structures (pentasil structure), as ZSM-5, ZSM-11 and ZSM-10.They have SiO 2The common basic structural unit of the five-ring form that tetrahedron constitutes.They have high SiO 2/ Al 2O 3Ratio, its aperture is between A type zeolite and X or y-type zeolite.
The same an acidic catalyst that is suitable for is a heteropolyacid, and different with isopoly-acid as inorganic polyacid, they have at least two different central atoms.The example that can mention is phospho-wolframic acid H 3PW 12O 40XH 2O and phospho-molybdic acid H 3PMo 12O 40XH 2O.Also can use catalyzer and the catalyst composition of in EP-A 158 229, mentioning in principle.
Preferred heteropolyacid is the heteropolyacid of molybdenum or tungsten and phosphoric acid, telluric acid, selenic acid, arsenic acid, silicic acid, particularly with the heteropolyacid of phosphoric acid.
The proton of heteropolyacid can partly be substituted by metal ion, and in this case, alkalimetal ion and alkaline-earth metal ions are preferred.
Acid ion exchangers is as crosslinked polystyrene or the acidic metal oxide such as the SiO of band sulfo group 2, Al 2O 3, ZrO 2, TiO 2, SuO 2, TiO 2Deng or the composition of single oxide compound also be suitable for.Also available mineral acid of oxide compound such as vitriolization are to improve strength of acid.
Mineral acid such as sulfuric acid and phosphoric acid and organic acid such as sulfonic acid also are suitable for and make an acidic catalyst.
If reaction was carried out with two steps, the temperature in the present invention's second reactions steps remains on 30-300, preferred 40-280, particularly 60-250 ℃.
Depend on selected system, reaction pressure may have decline slightly or raise.Usually, reaction pressure is 0.1-10, preferred 0.5-5, particularly 0.8-4 crust.
Reaction product can preferably be removed from homogeneous reaction mixture by inert gas.
Reaction product THF separates with traditional method with alcohol, preferably separates with distillation method.
Another possible method of finishing the inventive method is the combination of single stage method and two-step approach.In this case, be possible by conversion fully at the 4-alkoxyl group butanols that does not change into THF and alcohol under the single stage method condition fully under the condition of the present invention, in second step.
In addition, the invention still further relates to 1 of independent preparation formula III, 4-butyleneglycol monoether
HO-CH 2-CH 2-CH 2-CH 2-OR III, in the formula, R has the implication shown in formula I and the II, under this occasion, 1 of formula I and/or II, 4-butylene glycol diether as claim 1 is desired with water with hydrogen is left at hydrogenation catalyst, reaction under 20-300 ℃, 1-300 crust.
The hydrogenation catalyst that is fit to is that further catalysis generates the reaction of tetrahydrofuran (THF) and do not have acidity or above-mentioned all catalyzer of basic center.The butyleneglycol monoether of formula III is valuable intermediate, is used as C in synthetic active substance and plastics 4Elementary cell.
In addition, the invention still further relates to a kind of novel method, the 2-butylene alcohol ether of its Chinese style IV with transposition method preparation formula I raw material
CH 3-CH=CH-CH 2-OR IV, R have formula I and the described implication of II, change into 1 of butylene and formula I in the presence of metathesis catalyst, 4-butylene glycol diether
RO-CH 2-CH=CH-CH 2-OR I, R has the implication that above-mentioned formula I provides in the formula, and condition is that two R have identical meanings.
Reaction is by the carrying out shown in the following diagram, and 1,4-dialkoxy butylene is generated by the 1-alkoxybutenes by the method for cancellation 2-butylene in the presence of catalyzer: (equation 1)
Be used for metathesis catalyst of the present invention and can make the catalyzer of alkene by transposition shown in the reaction equation 2 for those
Figure C9719205400112
(equation 2)
The metathesis catalyst that is fit to is the homogeneous phase compound and the heterogeneous compound of transition metal, particularly periodic table of elements IV, VI, VII and VIII subgroup metal, and the homogeneous catalyst and the heterogeneous catalyst that contain these compounds.The example of such catalyzer document have description (as G.W.Parshall, S.D.Illd, homogeneous catalysis, the 2nd edition, 1992, Wiley, 217 pages are backward; R.L.Banks, catalysis, volume, 100 pages are backward; R.H.Grubbls, the inorganic chemistry progress is rolled up 24,1 pages backward).
Preferred catalyzer is that Grubbs disclosed general formula in WO 93,20111 is RuX 2(=CHR) (PR ' 3) 2Or RuCl 2(=CHR) (PR ' 3) 2Ruthenium compound, X is a halogen in the formula, R is hydrogen, alkyl or aryl, R ' is an alkyl.Formula [Ru (η 6-arene) X 2] 2/ (PR 3)/N 2The mixture of CHR ' compound also is suitable and preferred, it is as the suitability of the metathesis catalyst chemical association magazine at Neols, chemical communication, 1995,1127 pages of middle backward descriptions, arene for example is benzene, sym-trimethylbenzene or isopropyl benzene in the formula, and X is a halogen, and R is that alkyl and R ' are hydrogen, alkyl, aryl or trimethyl silyl.Formula (RuX 2(η 6-to isopropyl benzene) PCy 3)/N 2The compound of CHR ' also is suitable for as metathesis catalyst, and X is a halogen in the formula, and Cy is a cyclohexyl, and R ' is hydrogen, alkyl, aryl or trimethyl silyl.
Complex compound RuCl 2(the PCy of (=CHPh) 3) 2(Cy=cyclohexyl) and based on the compound that is purchased (Ru (η 6-to isopropyl benzene) Cl 2) 2/ PCy 3/ N 2CHSiMe 3Catalyst system be particularly preferred.Also can use its reaction product, be complex compound (Ru (η 6-to isopropyl benzene) (PCy 3) Cl 2) replacement component Ru (η 6-to isopropyl benzene) Cl 2And PCy 3
US 5,342 985 (DE 39 40 196A) and chemical association magazine, chemical communication (1979) 330-331 page or leaf has been described at heterogeneous Re compound as in the presence of the metathesis catalyst, by cancellation ethene, synthesize 1 by corresponding allyl ethers, 4-dialkoxy butylene.
But, known by document, the compound of transistion metal compound, particularly ruthenium can make unsaturated ethers as allyl ethers and butenyl ether by isomerization shown in the reaction equation 3.In the presence of water, carry out ether then and decompose, generate corresponding aldehyde.
Figure C9719205400121
(equation 3)
So, it is shocking, in the presence of the Ru compound, 1-alkoxyl group-the 2-butylene that is not easy metathesis reaction (comparing with allyl ethers) in principle can not become 1-alkoxyl group-1-butylene by isomery, on the contrary, and but by the cancellation 2-butylene, selectivity has generated 1,4-dialkoxy butylene.
Because compare with using dibromo butene, metathesis reaction is a favourable alternative method on industrial and environment, and using the butyleneglycol diether by the metathesis preparation is preferred as the precursor that the present invention prepares tetrahydrofuran (THF).
Explain method of the present invention with following embodiment, but limitation of the present invention anything but.Analyze with vapor-phase chromatography.The purity of the dibutoxy butylene of Shi Yonging is about 98% in an embodiment.
Embodiment 1
(by CuO, copper content is about 10% with 200ml copper/activated-carbon catalyst; On the 4mm activated charcoal pellets; Copper is coated with as amide) in the 200ml tubular reactor of packing into, then under about 180 ℃, activate in the hydrogen stream.In hydrogen stream (40l/h), 1 crust, under 230 ℃ with two kinds of chargings by catalyst section, charging is solution (11g/h) and the 11g/h water of 10% (weight) dibutoxy-2-butylene in propyl carbinol, every kind of charging is a gaseous state.Reaction effluent is two-phase.Per hour sampling at interval, and use gas chromatographic analysis.Organic phase contains (by anhydrous calculating) 95-98% propyl carbinol and about 0.8%THF.Water contains (by anhydrous calculating) 95% propyl carbinol and about 0.5%THF. Embodiment 2
(Re is as Re for about 6% (weight) of Re content, 4mm activated charcoal pellets with 200ml rhenium/activated-carbon catalyst 2O 7Coating) 300 ℃ of activation down, as among the embodiment 1.Make about 12g/h dibutoxy-2-butylene and about 11g/h water pass through catalyzer with 25l/h hydrogen carrier gas stream down at 220 ℃ then.Effluent contains 59% butanols and 30%THF.
Embodiment 3(two-step approach preparation)
A) (TPP) with 5g dibutoxy-2-butylene, 5g water, 0.1g HRuCl (CO) 3Pack in the 72ml metal high pressure autoclave with 0.05g TPP (triphenylphosphine), inject 50 crust hydrogen then.Under agitation autoclave is heated to 150 ℃, 2 hours postcooling.Residual voltage is 40 crust.The two-phase effluent of reaction is homogenized with 13g methyl alcohol, so that analyze.Discovery have an appointment 80%4-butoxy butanols and about 17% butanols.
B) 10g powders A l2O3 and 18g 4-butoxy butanols are sent into the bottom of distillation plant, and be heated to 175 ℃.Under this temperature, steam reaction product.With the fresh 4-butoxy butanols of product boil-up rate continuous supplementation.Distillment contains have an appointment 3% precursor, 52% butanols and 45%THF.
Embodiment 4(preparing the dialkoxy butylene) by metathesis
Under argon atmospher, in Glass Containers with 41mg RuCl 2(the PCy of (=CHPh) 3) 2(Cy=cyclohexyl) mixes with 8.0g 1-butoxy-2-butylene, and mixture is at room temperature stirred.The butylene that generates in the reaction can be discharged by bubble counter.After 12 hours, with gas-chromatography (GC/MS coupling) analyze reaction mixture.Except starting compound, also identifying 1-butoxy-2-butylene (E and Z isomer are 51.6 and 18.6% (area)) and dibutyl ether (4.2% (area), 1,4-dibutoxy-2-butylene) E and Z isomer is 4.78 and 17.1% (area)) and 2-butylene (2.9% (area)).1,4-dibutoxy-1-butylene (0.7% (area)) is an accessory constituent.
Embodiment 5
Step is described in the embodiment 4, but uses (Ru (η 6-to isopropyl benzene) (PCy 3) Cl 2)/N 2CHSiMe 3As catalyzer.At 60 ℃ after following 12 hours, measure 1 with gas chromatographic column, 4-dibutoxy butylene (1.9 and 3.0% (area)).

Claims (9)

1. method for preparing tetrahydrofuran (THF), this method comprise, under 20-300 ℃, 1-300 crust, in the presence of catalyzer or catalyst composition, makes 1 of formula I and/or II, 4-butylene glycol diether
RO-CH 2-CH＝CH-CH 2-OR I
RO-CH 2-CH 2-CH=CH-OR II, with water and H-H reaction, in the formula, R is identical or different, is C 1-C 15Alkyl or cycloalkyl, C 6-C 12Aryl or C 7-C 15Aralkyl, catalyzer or catalyst composition contain to be had the hydrogenation ability and acid sites is arranged or the composition of basic center, and contains one or more elements or its compound in periodictable I, II or VI, VII, VIII subgroup or III, IV, the V main group element in hydrogenation component.
2. contain one or more elements in rhenium, copper or the ruthenium or its compound catalyzer according to the process of claim 1 wherein to use as hydrogenation component.
3. carry out according to the process of claim 1 wherein that reaction goes on foot by two:
A) in the first step, in the presence of hydrogenation catalyst, make butylene glycol diether and water and the H-H reaction of formula I and/or II, obtain corresponding 1,4-butyleneglycol monoether, and
B) under 40-280 ℃, in the presence of an acidic catalyst or basic catalyst, make 1, the cyclisation of 4-butyleneglycol monoether generates tetrahydrofuran (THF).
4. according to the process of claim 1 wherein that formula I compound prepares as follows, in the presence of metathesis catalyst, make the 2-butylene alcohol ether reaction of formula IV, generate butylene and corresponding 1,4-butylene glycol diether,
CH 3-CH=CH-CH 2In-OR IV the formula, R is C 1-C 15Alkyl or cycloalkyl, C 6-C 12Aryl or C 7-C 15Aralkyl.
5. according to the method for claim 4, wherein use the metathesis catalyst that contains ruthenium or ruthenium compound.
6. according to the method for claim 5, its Chinese style RuCl 2(=CHR) (PR ' 3) 2Compound as metathesis catalyst, R is hydrogen, alkyl or aryl in the formula, R ' is an alkyl.
7. according to the method for claim 5, its Chinese style (RuX 2(η 6-to isopropyl benzene) PCy 3)/N 2The compound of CHR ' is as metathesis catalyst, and X is a halogen in the formula, and Cy is a cyclohexyl, and R ' is hydrogen, alkyl, aryl or trimethyl silyl.
8. according to the method for claim 4, wherein in the presence of metathesis catalyst, 2-butylene alcohol ether 1-butoxy-2-butylene is changed into 2-butylene and 1,4-butylene glycol diether 1,4-dibutoxy butylene.
9. according to the method for claim 3, wherein the butylene glycol diether of formula I and/or formula II is changed under 20-300 ℃, 1-300 crust corresponding 1,4-butyleneglycol monoether.
CN97192054A 1996-06-05 1997-05-28 Process for preparing tetrahydrofuran from dialkoxybutenes Expired - Fee Related CN1116290C (en)

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